CN107029702A - Load carbon fiber felt catalyst material of manganese oxide and its preparation method and application - Google Patents
Load carbon fiber felt catalyst material of manganese oxide and its preparation method and application Download PDFInfo
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- CN107029702A CN107029702A CN201710271871.0A CN201710271871A CN107029702A CN 107029702 A CN107029702 A CN 107029702A CN 201710271871 A CN201710271871 A CN 201710271871A CN 107029702 A CN107029702 A CN 107029702A
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- Prior art keywords
- manganese oxide
- carbon fiber
- fiber felt
- preparation
- loaded
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 178
- 239000000463 material Substances 0.000 title claims abstract description 86
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 69
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 69
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 title abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 104
- 239000007921 spray Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 15
- 239000012286 potassium permanganate Substances 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910006364 δ-MnO2 Inorganic materials 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- PQQBWLKXIHCGRL-UHFFFAOYSA-N [O-2].[Mn+2].[C+4].[O-2].[O-2] Chemical compound [O-2].[Mn+2].[C+4].[O-2].[O-2] PQQBWLKXIHCGRL-UHFFFAOYSA-N 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000011572 manganese Substances 0.000 description 34
- 230000003647 oxidation Effects 0.000 description 24
- 238000007254 oxidation reaction Methods 0.000 description 24
- 239000000835 fiber Substances 0.000 description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 22
- 229910052748 manganese Inorganic materials 0.000 description 22
- 229910052799 carbon Inorganic materials 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 15
- 238000001354 calcination Methods 0.000 description 14
- 229910016978 MnOx Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- -1 Na+ Chemical class 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000012855 volatile organic compound Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 206010002091 Anaesthesia Diseases 0.000 description 1
- 208000000058 Anaplasia Diseases 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910003179 MnxCo3−xO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 description 1
- 230000037005 anaesthesia Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910003144 α-MnO2 Inorganic materials 0.000 description 1
- 229910006648 β-MnO2 Inorganic materials 0.000 description 1
- 229910006287 γ-MnO2 Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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- B01J37/32—Freeze drying, i.e. lyophilisation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The present invention relates to carbon fiber felt catalyst material of load manganese oxide and its preparation method and application, manganese oxide nanometer sheet is loaded on carbon fiber felt matrix using spraying process, the carbon fiber felt material of the load manganese oxide is obtained after drying.In the present invention, loaded the method for the carbon fiber felt material of manganese oxide have it is simple and easy to apply, it is environment-friendly, the features such as with low cost.
Description
Technical field
The invention belongs to environmental catalysis field, it is related to a kind of carbon fiber felt catalyst material for loading manganese oxide, especially relates to
And a kind of new, green, efficient crystallization catalyst and its preparation method and application for catalytic oxidation of low-concentration formaldehyde.
Background technology
Formaldehyde is a kind of typical harmful organic compounds.In recent years, due to the cheap chemical industry such as phenolic resin, Lauxite
Raw material is added into the product such as coating and sheet material adhesive extensively, and Formaldehyde Pollution of Indoor Air problem is increasingly serious.It is well known that first
Aldehyde has strong impulse, is a kind of teratogenesis carcinogenic substance, can also cause anesthesia disease and increase photochemical pollution.Therefore,
For health, formaldehyde is removed imperative.At present, it is required for outfit to go in air purifier, air-conditioning and VMC
Formaldehyde catalyst functional unit.
At present, the Main Means of formaldehyde are removed at room temperature includes absorption, plasma oxidation, catalysis oxidation (burning), light
Catalysis oxidation etc..Heat catalytic oxidation method is into CO using dynamical catalyst by VOCs catalytic degradations2And H2O, it has catalysis
The advantages of efficiency high, non-secondary pollution, easily-controlled operation, be a kind of technology of great prospect.Catalyst for removing VOCs
Mainly there are two kinds of catalyst of transition metal oxide and noble-metal-supported catalyst.Common transition group metallic oxide catalyst
There is Co3O4、MnOx、CeO2Deng.Noble metal catalyst has platinum, palladium, gold, silver etc., and they are generally loaded on transition metal oxide
Or on their mixture.Compared to noble metal catalyst, transition group metallic oxide catalyst substantially has cheap, storage
The advantages of measuring many.
In numerous transition metal oxides, the oxide of manganese is widely used in many due to the characteristic such as cheap, nontoxic
In catalytic reaction, such as CO oxidations.It is δ-MnO especially with Birnessite in numerous crystal formations of manganese oxide2Catalytic effect be
Good, it is with MnO6It is a number of hydrone and difference between the layer structure that regular octahedron is formed for group, manganese oxide layer
Cation (such as Na+、K+、Ca2+).Layer structure unique Birnessite becomes an effective catalyst and is used for
Remove carbon monoxide and VOC (VOC).Open to wait and find δ-MnO2Catalyst when removing formaldehyde than α, β and
γ-MnO2With higher catalytic activity.Apply et al. and to find MnxCo3-xO4Catalyst can be with complete catalysts oxidation first at 75 DEG C
Aldehyde, and catalyst life was up to 50 hours.Week et al. is successfully prepared MnO by infusion processx/ GAC catalyst, utilizes activity
Formaldehyde in the huge specific surface area absorption air of charcoal, improves the catalytic reaction efficiency of Mn oxide.But, that is reported grinds
The removal that work is mostly directed to high-concentration formaldehyde under static conditions is studied carefully, to (concentration of formaldehyde is less than close to Shi Jishiyong working condition
1ppm, high-speed) under be but rarely reported except the research of formaldehyde catalyst.
The content of the invention
For the removal of low concentration formaldehyde, the problem of acticarbon that solution is now used easily causes secondary pollution,
There is provided a kind of new catalyst of removal low concentration formaldehyde and preparation method thereof.
On the one hand, the invention provides a kind of preparation method for the carbon fiber felt material for loading manganese oxide, using spraying process
Manganese oxide nanometer sheet is loaded on carbon fiber felt matrix, the carbon fiber felt material of the load manganese oxide is obtained after vacuum drying
Material.
The present invention is, as spraying matrix, catalyst to be used as from manganese oxide nanometer sheet from active-carbon fibre material.Its
Middle activated carbon fiber material is to be piled up to form along fiber axial direction by organic fibers such as flake graphites, with micropore knot
Structure, relatively high specific surface area, abundant surface group is conducive to the absorption of formaldehyde gas, using the teaching of the invention it is possible to provide sufficient space and
Scattered avtive spot is used to react generation manganese oxide nanometer sheet enough.Wherein manganese oxide nanometer sheet is the good δ phases of crystallinity
Crystal structure.δ phase oxidations manganese is layer structure, is beneficial to provide more avtive spots for being catalyzed formaldehyde.
It is preferred that the parameter of the spraying process includes：Spray a diameter of 3~5mm, quantity for spray for 0.05~0.1g/ minutes,
Spray time 30~60 minutes.
It is preferred that the carbon fiber felt material that gained is loaded into manganese oxide is calcined 2~4 hours at 120~240 DEG C.Calcining
Manganese oxide surface defect is reduced after the bond strength of manganese oxide and carbon fiber, calcining can be increased, Mn4+Content increase, Mn2+
Content is reduced.
It is preferred that by ethanol, the reducing agent such as manganese sulfate is added drop-wise in liquor potassic permanganate, is stirred 12~24 hours at room temperature
Afterwards, suction filtration wash, then it is freeze-dried after obtain the manganese oxide nanometer sheet.
It is preferred that before spraying manganese oxide nanometer sheet, the manganese oxide nanometer sheet calcined at 120~240 DEG C to 2~
4 hours.
Also, it is preferred that the mol ratio of the reducing agent and potassium permanganate is (1~2)：1.
Also, it is preferred that the rate of addition of the reducing agent is 1~3ml/ minutes.
It is preferred that the reducing agent is selected from least one of ethanol, reproducibility weak acid, inorganic salts.
On the other hand, present invention also offers a kind of carbon fiber felt material of the load manganese oxide prepared according to above-mentioned method
Material, including carbon fiber felt matrix, and the manganese oxide being carried on the carbon fiber felt matrix, wherein manganese oxide are well-crystallized
δ-MnO2(that is, the good stratiform manganese oxide nanometer sheet material of crystallization).It is preferred that the manganese oxide nanometer sheet and carbon fiber felt
The mass ratio of matrix is (1.5~3)：(5~10).
Oxidation manganese material (manganese oxide) in the carbon fiber felt material of load manganese oxide prepared by the present invention is well-crystallized
δ-MnO2.Aoxidizing manganese material (manganese oxide) has mesopore orbit, and specific surface area is more than 100m2/g.Wherein, δ-MnO2For stratiform
The material of crystal structure.Contain multiple Mn valence states, higher low-temperature reduction and different surface oxygen species.
Another further aspect, present invention also offers a kind of carbon fiber felt material of the load manganese oxide prepared according to above-mentioned method
Expect the application in catalysis formaldehyde.
The carbon fiber felt material of load manganese oxide prepared by the present invention can remove low concentration formaldehyde gas as catalysis oxidation
Catalyst or VOC (VOC) gas catalyst, can be used as remove purifying formaldehyde piece (bag), it can also be used to sky
Gas purifier, air-conditioning and VMC remove formaldehyde catalytic purification.
Main advantages of the present invention are：
Catalyst mentioned by the present invention is a kind of carbon fibre material for having loaded δ phase oxidation manganese nanometer sheets, and wherein manganese oxide is received
Rice piece is the good δ phase crystal structures of crystallinity.δ phase oxidations manganese is layer structure, is beneficial to provide more avtive spots.
And there is loose structure as the carbon fibre material of matrix, be conducive to absorbing formaldehyde gas.Oxygen has been loaded mentioned by the present invention
Changing the carbon fibre material of manganese has multiple Mn ionic valence conditions, preferable low-temperature reduction and different surface oxygen species, and this is all
It is beneficial to the progress of catalytic oxidation.Finally, the preparation mentioned by the present invention has loaded the carbon fiber felt material of manganese oxide
Method, it is environment-friendly with simple and easy to apply, (by between liquor potassic permanganate and ethanol solution the features such as with low cost
Simple oxidation reduction reaction generation oxidation manganese material, then manganese oxide powder body material is coated to carbon fiber felt surface with spray gun, most
Optionally carry out calcining the carbon fibre material for obtaining loading manganese oxide afterwards).
Brief description of the drawings
Fig. 1 is the manganese oxide nanometer sheet MnO prepared by the embodiment of the present invention 12- ethyl XRD spectrum；
Fig. 2 is the XRD spectrum of the prepared different carbon fibre materials for having loaded manganese oxide and carbon fiber substrate material；
Fig. 3 is prepared MnOxThe SEM pictures of/CF samples；
Fig. 4 is prepared cal-MnOxThe SEM pictures of/CF samples；
Fig. 5 is prepared MnOxThe SEM pictures of-cal/CF samples；
Fig. 6 is prepared MnOxThe SEM pictures of-cal/CF samples；
Fig. 7 is nitrogen adsorption-desorption isothermal curve of the prepared different carbon fibre materials for having loaded manganese oxide；
Fig. 8 is the H of the prepared different carbon fibre materials for having loaded manganese oxide2- TPR collection of illustrative plates；
Fig. 9 is the O of the prepared different carbon fibre materials for having loaded manganese oxide2- TPD collection of illustrative plates；
Figure 10 is the XPS collection of illustrative plates of the prepared different carbon fibre materials for having loaded stratiform manganese oxide；
Figure 11 be the prepared different carbon fibre materials for having loaded stratiform manganese oxide remove formaldehyde when catalytic efficiency at any time
Between the collection of illustrative plates that changes.
Embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
Oxidation manganese material in the carbon fiber felt material for the load manganese oxide that the present invention is prepared by spraying process is knot
Brilliant good δ-MnO2, with mesopore orbit, its specific surface area is about 131.77m2/g；With layered crystal structure.The composite wood
Material has multiple Mn ionic valence conditions (such as Mn2+、Mn3+、Mn4+, wherein Mn2+Account for Mn total ion concentrations 10~15%, Mn3+Account for Mn
Total ion concentration 59~63%, Mn4+Account for Mn total ion concentrations 23~30%), preferable low-temperature reduction and different surfaces
Oxygen species.Wherein surface oxygen species refer specifically to manganese oxide surface adsorbed oxygen, and carbon fiber surface oxy radical and manganese oxide are brilliant
Lattice oxygen.
The spraying process that the present invention is selected is relative in situ synthesis, and the combination of manganese oxide and carbon fiber is more firm, meanwhile,
Experimental implementation is more simple, is easy to a large amount of preparations, for applying.Means of calcination is equally the combination of oxidation reinforced manganese and carbon fiber
The means of intensity.Illustrate to following exemplary the preparation side of the carbon fiber felt catalyst material for the load manganese oxide that the present invention is provided
Method.
Prepare manganese oxide nanometer sheet.Reducing agent is added drop-wise in liquor potassic permanganate, after stirring 12-24 hours at room temperature,
Suction filtration wash, then it is freeze-dried after obtain the manganese oxide nanometer sheet.Reducing agent can be ethanol or other tools
There are the weak acid or inorganic salts of reproducibility.The mol ratio of the reducing agent and potassium permanganate can be (1~2)：1.Wherein, the reduction
The rate of addition of agent can be 1~3ml/ minutes.In a preferred embodiment, in step (A), by 3.16g KMnO4
It is dissolved in 100mL water, is stirred vigorously to being completely dissolved, 1.95mL straight alcohol solution is then slowly dropped to KMnO4In solution,
The solution obtained is stirred at room temperature suction filtration after 24h and washed, freeze-dried rear acquisition manganese oxide nanometer sheet, is designated as MnO2-
ethyl.Wherein manganese oxide nanometer sheet is the good manganese oxide nanometer sheet material of crystallization.
It is dried after by spraying process, manganese oxide nanometer sheet is loaded on carbon fiber felt matrix.Wherein, the oxidation
The mass ratio of manganese nanometer sheet and carbon fiber felt matrix can be (1.5~3)：(5~10).The parameter of the spraying process may include：Spray
It is 0.05~0.1g/ minutes, spray time 30~60 minutes to apply a diameter of 3~5mm, quantity for spray.In a preferred embodiment party
In case, 1.5~3g MnO will be dispersed with2After-ethyl 100mL aqueous isopropanols ultrasound 30min, it is using jet diameters
0.3mm spray gun, is sprayed on 5~10g carbon fiber felt materials, is obtained and is carried on carbon fiber felt after being dried in vacuo through 30 DEG C
Aoxidize manganese material, referred to as MnOx/CF。
Calcined while the carbon fiber felt material selectivity of manganese oxide will be sprayed, obtain loading the carbon fiber felt material of manganese oxide
Material.Specifically, the carbon fiber felt material for gained being loaded into manganese oxide can calcine 2~4 hours that (the two is same at 120~240 DEG C
The two of the material of Shi Jinhang calcinings combines more close and firm, the increase of lattice oxygen content).As an example, gained is born
The carbon fiber felt material for carrying manganese oxide is calcined 2~4 hours at 120~240 DEG C.If before spraying manganese oxide nanometer sheet,
Only manganese oxide nanometer sheet is calcined and (calcined 2~4 hours at 120~240 DEG C) and is sprayed afterwards, no subsequent calcination；Or
Person is only calcined carbon fiber felt the spray for carrying out manganese oxide nanometer sheet after ((being calcined 2~4 hours at 120~240 DEG C)) again
Apply, equally without subsequent calcination, can not all realize the two while the effect above calcined.
Generally speaking, the present invention is prepared at room temperature using the simple oxidation reduction reaction between potassium permanganate and reducing agent
Manganese oxide nanometer sheet material, is coated on carbon fibre material, and optionally carry out by δ phase oxidation manganese materials followed by spray gun
Calcining, is prepared for loading the carbon fiber felt material of manganese oxide.
The carbon fiber felt material of load stratiform manganese oxide prepared by the present invention is used for catalytic elimination low concentration as catalyst
Formaldehyde gas.It is that concentration is estimated for 1ppm formaldehyde gas by removing flow velocity for 52L/min that its catalytic performance, which is characterized,
's.Experimentation is as follows：13g or so catalyst is cut into 25mm × 25mm square flaky material, is stacked up, is put into
Tested in sample bin.In whole course of reaction, sampled, and carried out with ammonium ferric sulfate solution with phenol reagent every 0.5-1h
After chromogenic reaction, content of formaldehyde is detected using ultraviolet spectrometer.
The manganese oxide nanometer sheet of the present invention is the δ phase oxidation manganese of well-crystallized, with layered crystal structure, larger ratio table
Area (>100m2/ g) and meso-hole structure.The carbon fiber felt material of load manganese oxide prepared by the present invention contains the manganese of multiple valence state
(Mn2+, Mn3+And Mn4+), preferable low-temperature reduction and abundant surface oxygen species (manganese oxide surface adsorbed oxygen, carbon fiber
Surface oxygen-containing groups and manganese oxide Lattice Oxygen).When the catalyst for removing low concentration formaldehyde, material PARA FORMALDEHYDE PRILLS(91,95) in 9h
Catalytic efficiency it is higher, can partly maintain more than 50% always, and effectively catalysis time is up to more than 27h.The catalyst
Preparation method is simple and easy to apply, environmentally friendly, with low cost, it can also be used to the catalysis of VOC (VOC) gas
Purification.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only that an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
The test method of unreceipted actual conditions in the following example in the present invention, generally according to normal condition, or is pressed
According to the condition proposed by manufacturer.Unless otherwise indicated, all percentage and number be by weight.
Embodiment 1
By 3.16g KMnO4It is dissolved in 100mL water, is stirred vigorously to being completely dissolved, it is then that 1.95mL straight alcohol solution is slow
It is added drop-wise to KMnO4In solution, the solution obtained is stirred at room temperature suction filtration after 24h and washed, freeze-dried to be aoxidized afterwards
Manganese nanometer sheet, is designated as MnO2-ethyl.In step (B), 1.5g MnO will be dispersed with2- ethyl 100mL aqueous isopropanols surpass
After sound 30min, using the spray gun that jet diameters are 0.3mm, spray on 5g carbon fiber felt materials, obtained after being dried in vacuo through 30 DEG C
The oxidation manganese material on carbon fiber felt, referred to as MnO must be carried onx/CF。
Embodiment 2
In order to examine calcining to remove the influence of formaldehyde performance to catalyst, by 3.16g KMnO4It is dissolved in 100mL water, it is acute
1.95mL straight alcohol solution is then slowly dropped to KMnO by strong stirring to being completely dissolved4In solution, the solution obtained is in room
Suction filtration is washed after warm lower stirring 24h, freeze-dried rear acquisition manganese oxide nanometer sheet, is designated as MnO2-ethyl.In step (B)
In, 1.5g MnO will be dispersed with2The use of jet diameters is 0.3mm's after-ethyl 100mL aqueous isopropanols ultrasound 30min
Spray gun, is sprayed on 5g carbon fiber felt materials, and the oxidation manganese material being carried on carbon fiber felt is obtained after being dried in vacuo through 30 DEG C,
And 2h, referred to as cal-MnO are calcined at 200 DEG Cx/CF。
Embodiment 3
In order to examine calcining to remove the influence of formaldehyde performance to catalyst, by 3.16g KMnO4It is dissolved in 100ml water, it is acute
1.95mL straight alcohol solution is then slowly dropped to KMnO by strong stirring to being completely dissolved4In solution, the solution obtained is in room
Suction filtration is washed after warm lower stirring 24h, freeze-dried rear acquisition manganese oxide nanometer sheet, is designated as MnO2-ethyl.In step (C)
In, take 1.5g MnO2- ethyl materials, 2h is calcined at 200 DEG C.In step (B), 1.5g will be dispersed with by above-mentioned calcining
MnO afterwards2After-ethyl 100mL aqueous isopropanols ultrasound 30min, using the spray gun that jet diameters are 0.3mm, 5g is sprayed to
On carbon fiber felt material without calcining, the oxidation manganese material being carried on carbon fiber felt is obtained after being dried in vacuo through 30 DEG C, is claimed
For MnOx-cal/CF。
Embodiment 4
In order to examine calcining carbon fiber felt to remove the influence of formaldehyde performance to catalyst, by 3.16g KMnO4It is dissolved in 100mL
In water, it is stirred vigorously to being completely dissolved, 1.95mL straight alcohol solution is then slowly dropped to KMnO4In solution, obtained
Solution is stirred at room temperature suction filtration after 24h and washed, freeze-dried rear acquisition manganese oxide nanometer sheet, is designated as MnO2-ethyl.
In step (C), 5g carbon fiber felt materials are taken, 2h is calcined at 200 DEG C.In step (B), 1.5g MnO will be dispersed with2-
After ethyl 100mL aqueous isopropanols ultrasound 30min, using the spray gun that jet diameters are 0.3mm, spray in above-mentioned steps
On carbon fiber felt material by calcining, the oxidation manganese material being carried on carbon fiber felt is obtained after being dried in vacuo through 30 DEG C, and
Referred to as MnOx/CF-cal。
Fig. 1 is prepared manganese oxide nanometer sheet MnO2- ethyl XRD spectrum.As seen from Figure 1, the manganese oxide nanometer sheet
For the δ-MnO of crystallization2(JCPDS 80-1098), wherein 2 θ=12.5 °, 25 °, 36.5 ° and 65.5 ° correspond respectively to (001),
(002), (- 111) and (- 321) crystal face.This illustrates that we are successfully prepared for high-specific surface area (＞ 100m2g-1) δ phases
Stratiform manganese oxide nanometer sheet.
Fig. 2 is the XRD spectrum of the prepared different carbon fibre material for having loaded manganese oxide and carbon fiber substrate material.
From Figure 2 it can be seen that having loaded the δ-MnO of crystallization in carbon fiber substrate2(JCPDS 80-1098), wherein 2 θ=12.5 °, 25 °,
36.5 ° and 65.5 ° correspond respectively to (001), (002), (- 111) and (- 321) crystal face.This illustrates success on this explanation carbon fiber
Oxidation manganese material is loaded.
Fig. 3-6 is the SEM pictures of the prepared different carbon fibre materials for having loaded manganese oxide.A, b, c are in Fig. 3
MnOxThe SEM spectrum of/CF samples, it can be found that carbon fiber surface generates the MnO of uniform loadx, and have agglomeration；
A, b, c are cal-MnO in Fig. 4xThe SEM spectrum of/CF samples, it can be found that the MnO of carbon fiber surface2Agglomeration is more serious,
There is duct generation on surface；A, b, c are MnO in Fig. 5xThe SEM spectrum of-cal/CF samples, it can be found that the MnO of carbon fiber surfacexCompared with
It is not serious for uniform agglomeration；A, b, c are MnO in Fig. 6xThe SEM spectrum of-cal/CF samples, it can be found that fiber surface
MnOxIt is more uniform, with part agglomeration.
Fig. 7 is nitrogen adsorption-desorption isothermal curve of the prepared different carbon fibre materials for having loaded manganese oxide.
N2The relative pressure range of adsorption isotherm is shown to be mesoporous material in 0.1-1.0.And its specific surface area be respectively 24.35,
12.46、27.66、19.43m2g-1, its aperture is respectively 24,33,22,31nm.
Fig. 8 is the H of the prepared different carbon fibre materials for having loaded manganese oxide2- TPR collection of illustrative plates.At low temperature
Peak corresponds to Mn4+To Mn3+Conversion, peak at high temperature corresponds to Mn3+To Mn2+Conversion.Can be with by the relative position at peak
Find out, the sample of embodiment 2 has best low-temperature reduction, be conducive to the progress of catalytic reaction.
Fig. 9 is the O of the prepared different carbon fibre materials for having loaded manganese oxide2- TPD collection of illustrative plates.At low temperature
Peak corresponds to Adsorbed oxygen species, positioned at the peak of middle-temperature section for carbon fiber surface oxy radical oxygen species, the peak at high temperature
Corresponding to Lattice Oxygen.
Figure 10 is the XPS collection of illustrative plates of the prepared different carbon fibre materials for having loaded stratiform manganese oxide, wherein a, b, c, d
The XPS collection of illustrative plates of the carbon fibre material for having loaded stratiform manganese oxide prepared by embodiment 1,2,3,4 is represented respectively.642.2eV and
653.6eV peak corresponds respectively to Mn 2p3/2 and Mn 2p1/2.Mn2p3/2 peak can be divided into Mn2+, Mn3+And Mn4+, respectively
Corresponding to 641eV, 642eV and 644eV, its each shared ratio be located in table 3.Oxygen in table 3, embodiment 2
Change manganese Mn2+Shared ratio is minimum, and Mn4+Shared ratio is up to 29.34%, due to Mn4+Oxidisability it is most strong, contain
The Mn of higher proportion4+Catalyst its catalytic performance it is more preferable.Except Mn2+And Mn4+, the manganese oxide in the present embodiment also contains Mn3 +, Mn3+Presence have progress beneficial to formaldehyde catalytic reaction, this is due to Mn3+/Mn4+Conversion can be less than Mn4+/Mn2+。
Table 1 is MnO2The mesoporous parameter of-ethyl nanometer sheets：
Table 2 is the mesoporous parameter of the carbon fiber felt material for having loaded manganese oxide nanometer sheet prepared by embodiment 1-4：
Table 3 is each valence state in the Mn contents of the embodiment 1-4 carbon fiber felt materials for having loaded manganese oxide nanometer sheet prepared
Shared ratio：
Effect example
The removal experiment of formaldehyde is carried out in a dynamic condition.Gas flow rate is 52L/min, and concentration of formaldehyde is 1ppm, catalysis
Agent consumption is 10g.The removal efficiency of formaldehyde is calculated according to below equation and obtained：Removal efficiency=(CEntrance-COutlet)/CEntrance.Figure
The a catalytic efficiencies that are the prepared different carbon fibre materials for having loaded stratiform manganese oxide when removing formaldehyde anaplasia at any time in 11
The collection of illustrative plates of change, it can be seen that this several sample catalytic efficiency of PARA FORMALDEHYDE PRILLS(91,95) in 9h is higher, and 50% can be partly maintained always
More than.B is the cal-MnO prepared by embodiment 2 in Figure 11x/ CF samples catalytic efficiency when removing formaldehyde is changed over time
Collection of illustrative plates, it can be found that the initial formaldehyde catalytic efficiency of the sample is higher, more than 80%, and effectively catalysis time up to 27h with
On.
All documents referred in the present invention are all incorporated as reference in this application, independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned instruction content of the present invention has been read, those skilled in the art can
To be made various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (10)
1. a kind of preparation method for the carbon fiber felt material for loading manganese oxide, it is characterised in that received manganese oxide using spraying process
Rice piece is loaded on carbon fiber felt matrix, and the carbon fiber felt material of the load manganese oxide is obtained after drying.
2. preparation method according to claim 1, it is characterised in that the parameter of the spraying process includes：Jet diameters are 3
~5mm, quantity for spray are 0.05~0.1g/ minutes, spray time 30~60 minutes.
3. preparation method according to claim 1 or 2, it is characterised in that gained is loaded to the carbon fiber felt material of manganese oxide
Material is calcined 2~4 hours at 120~200 DEG C.
4. the preparation method according to any one of claim 1-3, it is characterised in that reducing agent is added drop-wise to potassium permanganate
In solution, at room temperature stir 12~24 hours after, suction filtration washing, then it is freeze-dried after obtain the manganese oxide nanometer sheet.
5. preparation method according to claim 4, it is characterised in that the mol ratio of the reducing agent and potassium permanganate is（1
~2）：1.
6. the preparation method according to claim 4 or 5, it is characterised in that the rate of addition of the reducing agent is 1~3
Ml/ minutes.
7. the preparation method according to any one of claim 4-6, it is characterised in that the reducing agent is selected from ethanol, gone back
At least one of originality weak acid, inorganic salts.
8. a kind of carbon fiber felt material of load manganese oxide prepared by method according to any one of claim 1-7, it is special
Levy and be, including carbon fiber felt matrix, and the manganese oxide being carried on the carbon fiber felt matrix, wherein manganese oxide is crystallization
Good δ-MnO2。
9. the carbon fiber felt material of stratiform manganese oxide is loaded according to claim 8, it is characterised in that the load manganese oxide
Carbon fiber felt material specific surface area be 12~30 m2/ g, a diameter of 20~35 nm of mesopore orbit.
10. a kind of application of carbon fiber felt material of load manganese oxide as claimed in claim 8 or 9 in catalysis formaldehyde.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410148A (en) * | 2001-09-26 | 2003-04-16 | 区峰 | Regeneration type harmful gas filter and its filtering material |
| WO2012167280A1 (en) * | 2011-06-03 | 2012-12-06 | The Regents Of The University Of California | Manganese oxide and activated carbon fibers for removing particle, voc or ozone from a gas |
| CN105056948A (en) * | 2015-08-07 | 2015-11-18 | 河北亚太环境科技发展股份有限公司 | Ozone elimination catalyst with porous substrate as carrier and preparation method thereof |
| CN106268799A (en) * | 2016-08-26 | 2017-01-04 | 中国科学院上海硅酸盐研究所 | Manganese oxide nanometer sheet material of the crystallization of supporting Pt and its preparation method and application |
-
2017
- 2017-04-24 CN CN201710271871.0A patent/CN107029702B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410148A (en) * | 2001-09-26 | 2003-04-16 | 区峰 | Regeneration type harmful gas filter and its filtering material |
| WO2012167280A1 (en) * | 2011-06-03 | 2012-12-06 | The Regents Of The University Of California | Manganese oxide and activated carbon fibers for removing particle, voc or ozone from a gas |
| CN105056948A (en) * | 2015-08-07 | 2015-11-18 | 河北亚太环境科技发展股份有限公司 | Ozone elimination catalyst with porous substrate as carrier and preparation method thereof |
| CN106268799A (en) * | 2016-08-26 | 2017-01-04 | 中国科学院上海硅酸盐研究所 | Manganese oxide nanometer sheet material of the crystallization of supporting Pt and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| YU HU, ET AL: "Facile chemical synthesis of nanoporous layered ı-MnO2 thin film for high-performance flexible electrochemical capacitors", 《APPLIED SURFACE SCIENCE》 * |
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| CN115382387A (en) * | 2022-08-03 | 2022-11-25 | 厦门中创环保科技股份有限公司 | Manufacturing process of formaldehyde-removing felt and formaldehyde-removing felt |
| CN115382387B (en) * | 2022-08-03 | 2024-05-24 | 厦门中创环保科技股份有限公司 | Process for manufacturing formaldehyde-removing felt and formaldehyde-removing felt |
| CN116586049A (en) * | 2023-06-28 | 2023-08-15 | 南通大学 | Preparation method of all-silicon molecular sieve glass fiber composite material |
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